WO2023233724A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2023233724A1
WO2023233724A1 PCT/JP2023/005511 JP2023005511W WO2023233724A1 WO 2023233724 A1 WO2023233724 A1 WO 2023233724A1 JP 2023005511 W JP2023005511 W JP 2023005511W WO 2023233724 A1 WO2023233724 A1 WO 2023233724A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
secondary battery
active material
negative electrode
electrolyte secondary
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PCT/JP2023/005511
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English (en)
Japanese (ja)
Inventor
健太 合庭
彰 中村
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オルガノ株式会社
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Publication of WO2023233724A1 publication Critical patent/WO2023233724A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • a lithium-based electrolyte such as lithium hexafluorophosphate (LiPF 6 ) or phosphorus hexafluoride is used as a nonaqueous electrolyte in an organic nonaqueous solvent.
  • LiPF 6 lithium hexafluorophosphate
  • phosphorus hexafluoride phosphorus hexafluoride
  • a non-aqueous electrolyte in which a sodium-based electrolyte such as sodium chloride (NaPF 6 ) is dissolved is used.
  • the styrenic resin may be a copolymer with other copolymerizable vinyl monomers, as long as the main component is a single or copolymer of styrene or a styrene derivative.
  • examples include divinylbenzenes such as o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene, alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate.
  • Examples include polyfunctional monomers, (meth)acrylonitrile, methyl (meth)acrylate, and the like.
  • ethylene glycol di(meth)acrylate polyethylene glycol di(meth)acrylate having an ethylene polymerization number of 4 to 16, and divinylbenzene are more preferable; ) Acrylate is more preferred, and divinylbenzene is even more preferred.
  • Examples of the weakly basic anion exchange group represented by the above general formula (I) include a dimethylamino group, a diethylamino group, a dipropylamino group, and a dimethylamino group is preferred.
  • * indicates a bonding site between the weakly basic anion exchange group represented by the above general formula (I) and the substrate or a bonding group for bonding to the substrate.
  • the ring structure in the above general formula (III) can include a ring structure having 4 to 6 carbon atoms, and specifically, the ring structure in the following formula (IV) Examples include the pyridine ring represented by
  • the negative electrode of the non-aqueous electrolyte secondary battery according to the present invention is not particularly limited, but for example, a current collector may be a slurry of a negative electrode active material, a binder, a thickener, a conductive material, etc. with a solvent. Examples include those coated on a current collector and dried to form a sheet, and those made by slurrying a negative electrode active material, a conductive material, etc. with a solvent and coating it on a current collector.
  • the thickener for the negative electrode for example, carboxymethyl cellulose (CMC), methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, etc. are used, but the thickener is not limited thereto.
  • the amount of thickener used in the negative electrode is preferably 0 to 5 parts by weight based on 100 parts by weight of the negative electrode active material. Copper, nickel, stainless steel, nickel-plated steel, etc. are usually used for the negative electrode current collector.
  • the conductive material for the negative electrode include, but are not limited to, graphite, carbon black such as acetylene black and Ketjen black, fine particles of amorphous carbon such as needle coke, and carbon nanofibers.
  • a separator is used between the positive electrode and the negative electrode.
  • a commonly used microporous polymeric film can be used without particular limitation.
  • the film include polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide, polypropylene oxide, and the like.
  • [Half cell B] ⁇ Positive electrode> Active material: LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) Conductive aid: acetylene black (AB), graphite binder: polyvinylidene fluoride (PVDF) Active material layer mass ratio: NCM811/AB/graphite/PVDF 100/3/3/3 Current collector: Aluminum Coated surface dimensions: 30mm x 30mm Except for the above points, the configuration was the same as that of half cell A.
  • the following weakly basic anion exchange resin was prepared as an HF removal material.
  • Base Styrene-divinylbenzene copolymer with three-dimensional network structure
  • half cell A is used as the basic configuration. That is, a half cell with the same specifications as half cell A was prepared, except that a positive electrode was used in which an active material layer was formed by mixing 0.1 part by mass of a weakly basic anion exchange resin with 100 parts by mass of the positive electrode active material. (See Figure 2).
  • half cell A is used as the basic configuration. That is, a half cell with the same specifications as half cell A was fabricated, except that a positive electrode in which an active material layer was formed by mixing 1 part by mass of a weakly basic anion exchange resin with 100 parts by mass of the positive electrode active material was used (Fig. (see 2).
  • half cell B has a basic configuration. That is, a half cell with the same specifications as half cell B was prepared, except that a positive electrode was used in which an active material layer was formed by mixing 0.1 part by mass of a weakly basic anion exchange resin with 100 parts by mass of the positive electrode active material. (See Figure 2).
  • half cell C is used as the basic configuration. That is, a half cell with the same specifications as Half Cell C was produced, except that a negative electrode was used in which an active material layer was formed by mixing 0.1 part by mass of a weakly basic anion exchange resin with 100 parts by mass of the negative electrode active material. (See Figure 3).
  • half cell C is used as the basic configuration. That is, a half cell with the same specifications as half cell C was fabricated, except that a negative electrode was used in which an active material layer was formed by mixing 1 part by mass of a weakly basic anion exchange resin with 100 parts by mass of the negative electrode active material (Fig. (See 3).
  • half cell A is used as the basic configuration. That is, a half cell with the same specifications as half cell A was fabricated, except that a positive electrode in which an active material layer was formed by mixing 1 part by mass of a weakly basic anion exchange resin with 100 parts by mass of the positive electrode active material was used (Fig. (see 2).
  • the following weakly basic anion exchange resin was prepared as an HF removal material.
  • Base Styrene-divinylbenzene copolymer with three-dimensional network structure
  • Table 2 shows the charge/discharge test results for each full cell. From the results in Table 2, it was confirmed that in the comparison between Examples 8 and 9 and Comparative Example 5, the example using an electrode in which an active material layer was formed by mixing an HF removal material showed a higher capacity retention rate. It was done. These results demonstrated that the HF removal ability of the HF removal material has the effect of suppressing deterioration of battery performance (decrease in capacity retention rate).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne une batterie secondaire à électrolyte non aqueux dans laquelle un matériau d'élimination des HF est disposé et dont la capacité initiale ne diminue pas.　La batterie secondaire à électrolyte non aqueux selon la présente invention comprend une électrode positive, une électrode négative, un séparateur et une solution électrolytique non aqueuse, et est caractérisée en ce qu'un matériau d'élimination des HF est disposé dans la batterie secondaire à électrolyte non aqueux de telle sorte que le matériau d'élimination des HF est en contact avec l'électrode positive et/ou l'électrode négative. Le matériau d'élimination des HF est de préférence composé d'une résine échangeuse d'anions faiblement basique ; et il est préférable que la résine échangeuse d'anions faiblement basique soit disposée dans une couche de matériau actif de l'électrode positive ou de l'électrode négative. Il est également préférable que la résine échangeuse d'anions faiblement basique ait une structure de réseau tridimensionnel, tout en comprenant un groupe diméthylamino.
PCT/JP2023/005511 2022-05-31 2023-02-16 Batterie secondaire à électrolyte non aqueux WO2023233724A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-088429 2022-05-31
JP2022088429 2022-05-31

Publications (1)

Publication Number Publication Date
WO2023233724A1 true WO2023233724A1 (fr) 2023-12-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001223031A (ja) * 2000-02-09 2001-08-17 Ngk Insulators Ltd リチウム二次電池
JP2012009283A (ja) * 2010-06-24 2012-01-12 Fdk Corp リチウムイオン二次電池
JP2014179206A (ja) * 2013-03-14 2014-09-25 Sanyo Electric Co Ltd 非水電解質二次電池
JP2017188299A (ja) * 2016-04-05 2017-10-12 旭化成株式会社 非水系二次電池とそれに用いられる非水系電解液
JP2020068107A (ja) * 2018-10-24 2020-04-30 オルガノ株式会社 非水電解液の製造装置および非水電解液の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001223031A (ja) * 2000-02-09 2001-08-17 Ngk Insulators Ltd リチウム二次電池
JP2012009283A (ja) * 2010-06-24 2012-01-12 Fdk Corp リチウムイオン二次電池
JP2014179206A (ja) * 2013-03-14 2014-09-25 Sanyo Electric Co Ltd 非水電解質二次電池
JP2017188299A (ja) * 2016-04-05 2017-10-12 旭化成株式会社 非水系二次電池とそれに用いられる非水系電解液
JP2020068107A (ja) * 2018-10-24 2020-04-30 オルガノ株式会社 非水電解液の製造装置および非水電解液の製造方法

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